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WO2018198937A1 - Substrat transparent revêtu de film de revêtement, liquide de revêtement pour former un film de revêtement pour substrat transparent revêtu de film de revêtement, et procédé de production pour substrat transparent revêtu de film de revêtement - Google Patents

Substrat transparent revêtu de film de revêtement, liquide de revêtement pour former un film de revêtement pour substrat transparent revêtu de film de revêtement, et procédé de production pour substrat transparent revêtu de film de revêtement Download PDF

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Publication number
WO2018198937A1
WO2018198937A1 PCT/JP2018/016162 JP2018016162W WO2018198937A1 WO 2018198937 A1 WO2018198937 A1 WO 2018198937A1 JP 2018016162 W JP2018016162 W JP 2018016162W WO 2018198937 A1 WO2018198937 A1 WO 2018198937A1
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WO
WIPO (PCT)
Prior art keywords
transparent substrate
coating
film
coating liquid
mass
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2018/016162
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English (en)
Japanese (ja)
Inventor
瑞穂 小用
中澤　達洋
河津　光宏
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Sheet Glass Co Ltd
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Nippon Sheet Glass Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Sheet Glass Co Ltd filed Critical Nippon Sheet Glass Co Ltd
Priority to JP2019514445A priority Critical patent/JP7213177B2/ja
Publication of WO2018198937A1 publication Critical patent/WO2018198937A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C03C17/25—Oxides by deposition from the liquid phase
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/111—Anti-reflection coatings using layers comprising organic materials

Definitions

  • the present invention relates to a transparent substrate with a coating, a coating liquid for forming a coating of the transparent substrate with a coating, and a method for producing the transparent substrate with a coating.
  • a low reflection film is formed on the surface of a substrate such as glass or ceramic for the purpose of improving the function of the substrate in order to transmit more light or prevent glare due to reflection.
  • the low reflection film is used for glass for a vehicle, a show window or a glass plate used for a photoelectric conversion device.
  • a so-called thin film solar cell which is a kind of photoelectric conversion device, uses a glass plate in which a photoelectric conversion layer and a back thin film electrode made of a base film, a transparent conductive film, amorphous silicon, and the like are sequentially stacked. It is formed on the main surface opposite to the main surface, that is, the main surface on the side where sunlight enters.
  • the solar cell in which the low reflection film is formed on the sunlight incident side more sunlight is guided to the photoelectric conversion layer or the solar cell element, and the power generation amount is improved.
  • the most commonly used low-reflection film is a dielectric film formed by a vacuum deposition method, a sputtering method, a chemical vapor deposition method (CVD method), or the like. There is also.
  • the fine particle-containing film is formed by applying a coating liquid containing fine particles onto a transparent substrate by dipping, flow coating, spraying, or the like.
  • Patent Document 1 a coating liquid containing fine particles and a binder precursor is applied to a glass plate having surface irregularities by a spray method, dried at 400 ° C. and then 610 ° C.
  • the cover glass for photoelectric conversion devices formed by performing the baking process for 8 minutes is disclosed.
  • the coating formed on the cover glass can improve the average transmittance of light having a wavelength of 380 to 1100 nm by at least 2.37%.
  • Patent Document 2 a sol containing tetraethoxysilane, aluminum acetylacetonate, and colloidal silica is attached to a glass plate by a dip coating method, and heat treatment is performed at 680 ° C. for 180 seconds. A glass substrate coated therewith is disclosed. With the film formed on the glass substrate, the average transmittance of light having a wavelength of 300 to 1100 nm can be improved by 2.5%.
  • Patent Document 3 discloses colloidal silica having a dispersed particle size larger than the average primary particle size and having a shape factor and an aspect ratio of more than 1 to some extent, tetraalkoxysilane, A coated silicon substrate formed by applying a coating composition containing aluminum nitrate onto a substrate using a spin coater and performing a drying process at 100 ° C. for 1 minute is disclosed. Although there is no description about the improvement of the average light transmittance by this film, this film has a refractive index of 1.40 or less.
  • a transparent substrate with a coating such as a glass plate on which a coating is formed.
  • a transparent substrate with a coating has high alkali resistance so that it can be washed with a strong detergent as in the case of a float plate glass or the like without a coating.
  • the coated transparent substrate is also required to have improved alkali resistance. As described above, the coated transparent substrate has room for further improvement in terms of improving durability and alkali resistance.
  • an object of the present invention is to provide a coated transparent substrate having further improved durability and alkali resistance. Furthermore, another object of the present invention is to provide a coating solution for forming a film of such a transparent substrate with a film and a method for producing the transparent substrate with a film.
  • a first aspect of the present invention is a transparent substrate with a coating comprising a transparent substrate and a coating formed on at least one main surface of the transparent substrate,
  • the coating includes silica having a continuous structure, an aluminum compound, and an organic component, The content of the component in the coating is expressed in mass%, Silica having a continuous structure more than 93% to 99.9%
  • the aluminum compound is converted to Al 2 O 3 0.05 to less than 2%
  • the film thickness is 20 to 500 nm
  • the organic component comprises a beta keto ester;
  • a transparent substrate with a coating is provided.
  • the second aspect of the present invention is a coating liquid for forming a film of a transparent substrate with a film
  • the coating liquid includes a hydrolyzable silicon compound, an aluminum chelate complex, and a solvent
  • the hydrolyzable silicon compound is a compound represented by the formula (I): SiX 4 (where X is at least one selected from an alkoxy group, an acetoxy group, an alkenyloxy group, an amino group, and a halogen atom).
  • the aluminum chelate complex includes a polydentate ligand having a ⁇ -ketoester structure
  • the solvent includes an organic solvent that is miscible with water and has a boiling point of 70 ° C. or higher and lower than 180 ° C., When the mass of the silicon oxide component contained in the hydrolyzable silicon compound is 100 parts by mass when converted to SiO 2 , the aluminum chelate complex is 0.1 to 10 parts by mass.
  • Provide coating fluid When the mass of the silicon oxide component contained in the hydrolyzable silicon compound
  • the third aspect of the present invention is as follows.
  • a method for producing a coated transparent substrate according to the first aspect of the present invention The manufacturing method includes: An application step of applying a coating liquid for forming the film to the transparent substrate; A heating step of heating the transparent substrate coated with the coating liquid; Including The coating liquid is a coating liquid according to the second aspect of the present invention, In the heating step, the maximum temperature experienced by the surface of the transparent substrate is 350 ° C. or less, and the time that the surface of the transparent substrate is at a temperature of 150 ° C. or more is 5 minutes or less, A method for producing a coated transparent substrate is provided.
  • a coated transparent substrate with improved durability and alkali resistance can be provided.
  • the transparent substrate with a film according to the present embodiment includes a transparent substrate and a film formed on at least one main surface of the transparent substrate.
  • the film in the present embodiment includes silica having a continuous structure, an aluminum compound, and an organic component.
  • the coating has a physical thickness of 20 to 500 nm.
  • the physical thickness of the coating is preferably more than 100 nm and 500 nm or less, more preferably more than 100 nm and 150 nm or less.
  • the physical thickness of the coating is preferably 20 to 100 nm, and more preferably 50 to 90 nm.
  • the coating contains more than 93 mass% to 99.9 mass% (greater than 93 mass% and 99.9 mass% or less) of silica having a continuous structure.
  • Silica having a continuous structure is a silica that exists in a bulk shape in the coating and serves to shape the shape of the coating. Therefore, for example, when the coating includes silica fine particles, silica having a continuous structure is distinguished from the silica fine particles.
  • the silica having a continuous structure can also serve as a binder for binding the particulate components.
  • the silica network is sufficiently formed.
  • the content of silica having a continuous structure in the coating is preferably 97 to 99.8% by mass.
  • the content of the aluminum compound in the coating is 0.05 to less than 2% by mass (0.05% to less than 2% by mass) when the aluminum compound is converted to Al 2 O 3 , and 0.05 to 1 It is preferable that it is mass%.
  • the aluminum compound contained in the coating is preferably an aluminum chelate complex.
  • the film can improve durability and alkali resistance.
  • the aluminum chelate complex preferably contains a polydentate ligand having a ⁇ -ketoester structure.
  • An aluminum chelate complex containing such a multidentate ligand has high stability in a coating solution for forming a film.
  • the aluminum chelate complex may contain 1 or 2 alkoxy groups bonded directly to the aluminum atom.
  • the alkoxy group preferably has 1 to 8 carbon atoms, for example.
  • the alkoxy group may be, for example, any one selected from the group consisting of an i-propoxy group, an n-butoxy group, and a sec-butoxy group. It is considered that when the aluminum chelate complex contains an alkoxy group bonded directly to an aluminum atom, a crosslinked structure having aluminum as a central element can be introduced into the coating.
  • the carboxylic acid constituting the ester has 4 to 6 carbon atoms, and the alcohol constituting the ester has 1 to 3 carbon atoms. Is preferred. More preferably, in the ⁇ -ketoester structure, the carboxylic acid constituting the ester has 4 carbon atoms, and the alcohol constituting the ester has 2 carbon atoms.
  • Examples of the aluminum chelate complex contained in the film include ethyl acetoacetate, methyl acetoacetate, isopropyl acetoacetate, ethyl 3-oxopentanoate and ethyl 3-oxo-4-methylpentanoate as multidentate ligands.
  • Aluminum chelate complexes are preferably used.
  • the coating contains an organic component in the range of 0.05 to 5% by mass, and preferably in the range of 0.2 to 2% by mass.
  • This organic component contains a ⁇ -ketoester.
  • the organic component when the aluminum compound is an aluminum chelate complex, the organic component includes an organic component derived from a ligand of the aluminum chelate complex.
  • the organic component may contain an alkyl group.
  • the alkyl group may be, for example, a methyl group or an ethyl group.
  • the total content of silica, aluminum compound and organic component having a continuous structure in the coating is preferably 95% by mass or more.
  • the coating film may consist of only a silica having a continuous structure, an aluminum compound, and an organic component.
  • the film may contain other components other than silica having a continuous structure, an aluminum compound, and an organic component.
  • the coating may further contain inorganic fine particles.
  • the inorganic fine particles contained in the film may be inorganic fine particles other than silica fine particles, for example. Further, the coating may not contain inorganic fine particles.
  • a hydrolyzable silicon compound or a hydrolyzate of a hydrolyzable silicon compound can be used as a source of silica having a continuous structure.
  • the hydrolyzable silicon compound may include a compound represented by the following formula (I).
  • X is at least one selected from an alkoxy group, an acetoxy group, an alkenyloxy group, an amino group, and a halogen atom.
  • a hydrolyzable silicon compound typified by silicon alkoxide can be used as a supply source of silica having a continuous structure in the coating.
  • the silicon alkoxide include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, methyltriethoxysilane, methyltrimethoxysilane, ethyltriethoxysilane, and ethyltrimethoxysilane.
  • These hydrolyzable silicon compounds may be hydrolyzed and polycondensed by a so-called sol-gel method to form silica having a continuous structure.
  • Hydrolysis of the hydrolyzable silicon compound can be carried out as appropriate.
  • an acid and a base can be used for a hydrolysis catalyst
  • inorganic acids such as an acid, especially hydrochloric acid, nitric acid, a sulfuric acid, and phosphoric acid
  • hydrochloric acid it is preferable to use inorganic acids, such as an acid, especially hydrochloric acid, nitric acid, a sulfuric acid, and phosphoric acid.
  • hydrochloric acid is superior to the basic solution in terms of stability of the coating solution.
  • the hydrolysis catalyst it is desirable to use an acid having a high degree of ionization in an aqueous solution. Specifically, it is desirable to use an acid having an acid dissociation constant pKa (meaning a first acid dissociation constant when the acid is a polybasic acid) of 2.5 or less.
  • pKa meaning a first acid dissociation constant when the acid is a polybasic acid
  • the transparent substrate for example, a glass plate and a substrate made of an organic polymer are used.
  • substrate which consists of organic polymers the board
  • an example in which a glass plate is used as the transparent substrate will be described.
  • the glass plate is not particularly limited, but in order to smooth the surface of the coating provided on the main surface, a glass plate having excellent microscopic surface smoothness is preferable.
  • the glass plate may be a float plate glass having a smoothness with an arithmetic average roughness Ra of the main surface of, for example, 1 nm or less, preferably 0.5 nm or less.
  • the arithmetic average roughness Ra in the present specification is a value defined in JIS B0601-1994.
  • the glass plate may be a template glass having macroscopic irregularities of a size that can be confirmed with the naked eye.
  • the macroscopic unevenness means unevenness having an average interval Sm of about millimeter order, which is confirmed when the evaluation length in the roughness curve is set to centimeter order.
  • the average spacing Sm of the irregularities on the surface of the template glass is preferably 0.3 mm or more, more preferably 0.4 mm or more, particularly preferably 0.45 mm or more, 2.5 mm or less, further 2.1 mm or less, particularly 2.0 mm or less. In particular, it is preferably 1.5 mm or less.
  • the average interval Sm means the average value of the intervals of one mountain and valley obtained from the point where the roughness curve intersects the average line.
  • the surface irregularities of the template glass plate preferably have a maximum height Ry of 0.5 ⁇ m to 10 ⁇ m, particularly 1 ⁇ m to 8 ⁇ m, together with the average interval Sm in the above range.
  • the average interval Sm and the maximum height Ry are values specified in JIS (Japanese Industrial Standards) B0601-1994.
  • the arithmetic average roughness Ra can satisfy several nm or less, for example, 1 nm or less. Therefore, even a template glass can be suitably used as a transparent substrate of a transparent substrate with a film of this embodiment as a glass plate having excellent microscopic surface smoothness.
  • the glass plate may have the same composition as that of ordinary template glass or architectural glass plate, and preferably contains no coloring component as much as possible.
  • the content of iron oxide which is a typical coloring component, is preferably 0.06% by mass or less, particularly preferably 0.02% by mass or less in terms of Fe 2 O 3 .
  • the glass plate may be a glass plate in which another film is further formed on the main surface opposite to the main surface on which the film is formed.
  • the glass plate with a transparent conductive film is mentioned as a glass plate which can apply the film of this embodiment suitably.
  • This glass plate with a transparent conductive film has, for example, a transparent conductive film on one main surface of any of the glass plates described above, and has one or more underlayers such as fluorine-doped on the main surface of the glass plate.
  • the transparent conductive layer which has tin oxide as a main component is laminated
  • the transparent substrate with a coating according to the present embodiment described above can achieve high durability (particularly, durability evaluated by the following pressure cooker test) and high alkali resistance.
  • the transparent substrate with a film of the present embodiment includes, for example, an average transmittance in a wavelength range of 380 to 850 nm of the transparent substrate with a film after the pressure cooker test is performed, and the transparent substrate with a film before the pressure cooker test is performed.
  • the absolute value of the difference from the average transmittance in the wavelength region can be 1% or less, and can also be 0.6% or less.
  • the pressure cooker test refers to a transparent substrate with a film held at a temperature of 130 ° C., 2 atm, and a relative humidity of 100% for 1 hour at room temperature after releasing the applied pressure. It is a test in which the cycle of allowing to cool to 2 cycles is applied.
  • the transparent substrate with a film of the present embodiment is subjected to, for example, the average transmittance in the wavelength region 380 to 850 nm of the transparent substrate with a film after performing an alkali resistance test defined in JIS R3221: 2002, and the alkali resistance test is performed.
  • the absolute value of the difference from the average transmittance in the wavelength region of the transparent substrate with the previous film can be 0.8% or less, and can also be 0.5% or less.
  • the coated transparent substrate of this embodiment can have a transmittance gain of 1.5% or more, preferably 1.6% or more.
  • the transmittance gain in the present specification is an increase in the average transmittance in the wavelength region of the transparent substrate with the coating with respect to the average transmittance in the wavelength region 380 to 850 nm of the transparent substrate in a state where the coating is not formed. is there.
  • the transparent substrate with a film of this embodiment can be formed by applying a coating liquid on the main surface of a transparent substrate such as a glass plate to form a coating film, and drying and curing the coating film. That is, the coating film is formed by performing a heating process for drying and curing the coating film after the coating liquid for forming the coating film is applied to the transparent substrate.
  • the coating liquid in the present embodiment includes a hydrolyzable silicon compound, an aluminum chelate complex, and a solvent.
  • the hydrolyzable silicon compound in the coating liquid has the formula (I): SiX 4 (wherein X is at least one selected from an alkoxy group, an acetoxy group, an alkenyloxy group, an amino group, and a halogen atom). Contains the compound shown.
  • hydrolyzable silicon compounds include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane and tetraisopropoxysilane, methyltriethoxysilane, methyltrimethoxysilane, ethyltriethoxysilane, and ethyltrimethoxysilane.
  • the silicon alkoxide can be used.
  • the aluminum chelate complex in the coating solution contains a polydentate ligand having a ⁇ -ketoester structure.
  • the aluminum chelate complex may further comprise 1 or 2 alkoxy groups bonded directly to aluminum.
  • the alkoxy group preferably has 1 to 8 carbon atoms, for example.
  • the alkoxy group may be any one selected from the group consisting of an i-propoxy group, an n-butoxy group, and a sec-butoxy group. It is considered that when the aluminum chelate complex contains an alkoxy group bonded directly to an aluminum atom, a crosslinked structure having aluminum as a central element can be introduced into the coating.
  • the carboxylic acid constituting the ester has 4 to 6 carbon atoms and the alcohol constituting the ester has 1 to 3 carbon atoms. More preferably, in the ⁇ -ketoester structure, the carboxylic acid constituting the ester has 4 carbon atoms, and the alcohol constituting the ester has 2 carbon atoms.
  • Examples of the aluminum chelate complex in the coating solution include ethyl acetoacetate, methyl acetoacetate, isopropyl acetoacetate, ethyl 3-oxopentanoate and ethyl 3-oxo-4-methylpentanoate as multidentate ligands.
  • Aluminum chelate complexes are preferably used.
  • the solvent in the coating solution contains an organic solvent that is miscible with water.
  • This organic solvent includes those having a boiling point of 70 ° C. or higher and lower than 180 ° C.
  • ethanol (boiling point: 78 ° C.), 2-propanol (boiling point: 83 ° C.), 1-methoxy-2-propanol (boiling point: 121 ° C.), acetylacetone (boiling point: 141 ° C.), methoxypropyl acetate (boiling point: 146 ° C.) ), 3-methoxy-1-butanol (boiling point: 160 ° C.), diacetone alcohol (boiling point: 168 ° C.), 3-methoxy-3-methyl-1-butanol (boiling point: 174 ° C.), and the like.
  • the organic solvent has a boiling point of 70 ° C. or higher and lower than 180 ° C.
  • the organic solvent contains a solvent having a boiling point of 70 ° C. or higher and lower than 180 ° C. as a main component, and further includes a high boiling point organic solvent.
  • the organic solvent having a high boiling point those having a boiling point of 180 to 250 ° C. can be used. Thereby, the drying speed after coating can be delayed, and as a result, the leveling of the coating film is promoted, and the effects of reducing coating unevenness and homogenizing the appearance can be expected.
  • the amount of the organic solvent having a high boiling point is desirably 5% by mass or less based on the entire coating liquid.
  • high-boiling organic solvent examples include propylene glycol (boiling point: 187 ° C.), diethylene glycol monomethyl ether (boiling point: 193 ° C.), hexylene glycol (boiling point: 198 ° C.) and diethylene glycol (boiling point: 244 ° C.).
  • the aluminum chelate complex is 0.1 to 10 parts by mass.
  • the range is preferably 1 to 5 parts by mass.
  • the coating liquid in the present embodiment may further contain a hydrolysis catalyst for a hydrolyzable silicon compound.
  • a hydrolysis catalyst for a hydrolyzable silicon compound.
  • the hydrolysis catalyst either an acid or a base can be used. From the viewpoint of the stability of the coating solution, it is desirable to use an acid, particularly an inorganic acid, particularly hydrochloric acid. This is because acidic than basic is better in dispersibility of silica fine particles, and more excellent in the stability of the coating liquid.
  • As the hydrolysis catalyst it is desirable to use an acid having a high degree of ionization in an aqueous solution. Specifically, it is desirable to use an acid having an acid dissociation constant pKa (meaning a first acid dissociation constant when the acid is a polybasic acid) of 2.5 or less.
  • pKa meaning a first acid dissociation constant when the acid is a polybasic acid
  • any known method such as spin coating, roll coating, bar coating, dip coating, spray coating, or the like can be used.
  • Spray coating is excellent in terms of mass productivity.
  • Roll coating and bar coating are excellent in terms of homogeneity of the appearance of the coating film in addition to mass productivity.
  • the maximum temperature experienced by the surface of the transparent substrate is 350 ° C. or less, and the time during which the surface of the transparent substrate is at a temperature of 150 ° C. or more is 5 minutes or less. Is preferred. Moreover, it is preferable that the time in which the surface of the transparent substrate is at a temperature of 100 ° C. or higher is 30 seconds or longer in the heating step.
  • the present embodiment as described above, which includes an application step of applying a coating liquid for forming a coating on a transparent substrate, and a heating step of heating the transparent substrate to which the coating liquid has been applied.
  • the maximum temperature experienced by the surface of the transparent substrate is 350 ° C. or less
  • the time during which the surface of the transparent substrate is at a temperature of 150 ° C. or more is 5 minutes or less, preferably A production method wherein 130 ° C. or more is 5 minutes or less, Can be mentioned.
  • the following transparent substrates with a film according to aspects 1 to 7 can be mentioned.
  • a transparent substrate with a coating includes silica having a continuous structure and an aluminum compound, The content of the component in the coating is expressed in mass%, Silica having a continuous structure: 75 to 98% (preferably 75 to 95%, more preferably 80 to 92%) The aluminum compound is converted to Al 2 O 3 : 2 to 25% (preferably 5 to 25%, more preferably more than 8% to 20%) And The film thickness is 20 to 500 nm. Transparent substrate with coating.
  • a transparent substrate with a coating according to aspect 1 The aluminum compound is derived from an aluminum halide (preferably aluminum chloride) added to a coating solution for forming the film. Transparent substrate with coating.
  • an aluminum halide preferably aluminum chloride
  • a transparent substrate with a coating according to aspect 1 or 2 is derived from a hydrolyzable silicon compound or a hydrolyzate of a hydrolyzable silicon compound added to a coating solution for forming the film,
  • the hydrolyzable silicon compound is tetraalkoxysilane;
  • Transparent substrate with coating it is preferable that the transparent substrate with a film of aspect 3 consists of a silica and aluminum compound in which a film has a continuous structure.
  • a coated transparent substrate according to any one of the above aspects 1 to 3 A transmittance gain defined as an increase in the average transmittance of the transparent substrate with the coating in the wavelength region with respect to the average transmittance of the transparent substrate without the coating in the wavelength region of 380 to 850 nm is 1 .5% or more, Transparent substrate with coating.
  • a coated transparent substrate according to any one of the above aspects 1 to 4, The average transmittance in the wavelength range of 380 to 850 nm of the transparent substrate with the coating after performing the pressure cooker test on the transparent substrate with the coating, and the wavelength of the transparent substrate with the coating before performing the pressure cooker test
  • the absolute value of the difference from the average transmittance in the region is 1% or less (preferably 0.5% or less, more preferably 0.2% or less).
  • the pressure cooker test means that the coated transparent substrate is held for 1 hour under high temperature and high temperature conditions of 130 ° C., 2 atm and relative humidity of 100%, and after releasing the applied pressure, it is released to room temperature. This is a test in which the cycle of cooling is performed for two cycles.
  • a coated transparent substrate according to any one of the above aspects 1 to 5, The average transmittance in the wavelength range of 380 to 850 nm of the transparent substrate with the coating after performing the alkali resistance test defined in JIS R3221: 2002 on the transparent substrate with the coating, and the above before the alkali resistance test is performed.
  • the absolute value of the difference from the average transmittance in the wavelength region of the transparent substrate with a coating is 2% or less (preferably 1% or less, more preferably 0.5% or less).
  • Transparent substrate with coating stipulated in JIS R3221: 2002 is such that the transparent substrate with a coating is placed in contact with a sodium hydroxide solution having a temperature of 23 ° C. and a concentration of 1 mol / L so that the coating completely contacts the solution. It is a test immersed in time.
  • the thickness of the coating was determined using a photograph of a field emission scanning electron microscope (FE-SEM). The coating was observed with a field emission scanning electron microscope (S-4500, manufactured by Hitachi, Ltd.). From the FE-SEM photograph in the cross section from the upper side of the film at an angle of 30 °, the average value of the thickness of the coating at five measurement points was defined as the thickness of the coating.
  • FE-SEM field emission scanning electron microscope
  • Alkali resistance evaluation According to the alkali resistance test described in JIS R3221: 2002, the alkali resistance of the coated transparent substrate was evaluated. Specifically, the transparent substrate with a film was immersed in a 1 mol / L NaOH aqueous solution at 23 ° C. for 6 hours so that the film was completely in contact with the solution, then washed with water and dried. However, in this embodiment, instead of the absolute value of the difference in visible light transmittance defined in JIS R3221: 2002, the average transmission in the wavelength range of 380 to 850 nm measured by the same method as the evaluation of the transmission characteristics described above. The absolute value of the difference between the average transmittance after the alkali resistance test and the average transmittance before the alkali resistance test was carried out was determined as the alkali resistance evaluation.
  • Example 1 Preparation of coating solution> A mixture of 76.63 parts by weight of 1-methoxy-2-propanol (solvent), 5.03 parts by weight of water and 1.00 parts by weight of 1N hydrochloric acid (hydrolysis catalyst) was stirred and mixed with tetraethoxysilane (normal silicic acid). 17.34 parts by mass of ethyl (manufactured by Tama Chemical Co., Ltd.) was added, and the mixture was stirred for 8 hours while keeping the temperature at 40 ° C. to hydrolyze tetraethoxysilane to obtain a hydrolyzate A.
  • Hydrolyzed liquid A 60.00 g, 1-methoxy-2-propanol (solvent) 39.40 g, aluminum chelate complex solution (aluminum ethyl acetoacetate dibutoxide (“DX-9740” manufactured by Shin-Etsu Chemical Co., Ltd.)) at a concentration of 10 mass. %, Dissolved in 1-methoxy-2-propanol (solvent) so that the amount of the solution was 1%, the mixture was stirred and mixed to obtain the coating liquid of Example 1.
  • DX-9740 aluminum chelate complex solution
  • the silicon oxide component contained in the solid content of the coating solution is 98.82% by mass in terms of SiO 2
  • the aluminum compound in terms of Al 2 O 3 is 0.33% by mass
  • the organic component (aluminum chelate complex distribution) was 0.85% by mass.
  • the content rate of each component in solid content of a coating liquid is corresponded to the content rate of each component in the film formed. The same applies to the following examples and comparative examples.
  • Example 1 a coating was formed on the main surface on one side of the glass plate with a transparent conductive film to obtain a transparent substrate with a coating.
  • This glass plate is made of Nippon Soda Glass Co., Ltd., having a thickness of 3.2 mm, having a normal soda lime silicate composition, and having a transparent conductive layer including a transparent conductive layer formed on one main surface using an on-line CVD method. It was a glass plate with a transparent conductive film.
  • This glass plate is cut into 200 ⁇ 300 mm, immersed in an alkaline solution (alkaline cleaning solution LBC-1, manufactured by Reybold Co., Ltd.), cleaned with an ultrasonic cleaner, washed with deionized water, and dried at room temperature. Thus, a glass plate for forming a film was obtained.
  • an alkaline solution alkaline cleaning solution LBC-1, manufactured by Reybold Co., Ltd.
  • Example 1 using a roll coater, the coating liquid of Example 1 was applied to the main surface of the glass plate on which the transparent conductive film was not applied. At this time, the film thickness of the coating solution was adjusted to 1 to 5 ⁇ m. Next, the coating solution applied to the glass plate was dried and cured with hot air.
  • This hot air drying uses a belt-conveying hot air drying device, the hot air set temperature is set to 300 ° C., the distance between the hot air discharge nozzle and the glass plate is set to 5 mm, and the conveying speed is set to 0.5 m / min. This was performed by reciprocating four times and passing under the nozzle four times. At this time, the time during which the glass plate coated with the coating solution was in contact with hot air was 140 seconds.
  • Example 2 ⁇ Preparation of coating solution> Hydrolyzed liquid A, 1-methoxy-2-propanol (solvent), aluminum chelate complex solution, hydrolyzed liquid A 60.00 g, 1-methoxy-2-propanol (solvent) 39.85 g, aluminum chelate complex solution 0.15 g
  • a coating solution was prepared in the same manner as in Example 1 except that. In the coating solution, when the mass of the silicon oxide component contained in the hydrolyzable silicon compound converted to SiO 2 is 100 parts by mass, 0.5 parts by mass of the aluminum chelate complex is contained.
  • the silicon oxide component contained in the solid content of the coating solution is 99.70% by mass in terms of SiO 2
  • the aluminum compound in terms of Al 2 O 3 is 0.08% by mass
  • the organic component the distribution of the aluminum chelate complex.
  • the organic component derived from the ligand was 0.21% by mass.
  • Example 2 a coating film was formed in the same procedure as in Example 1 except that the coating liquid of Example 2 described above was used, and the above-described characteristics were evaluated. The results are shown in Table 1.
  • Example 3 ⁇ Preparation of coating solution> Hydrolyzed liquid A, 1-methoxy-2-propanol (solvent), aluminum chelate complex solution, hydrolyzed liquid A 60.00 g, 1-methoxy-2-propanol (solvent) 39.70 g, aluminum chelate complex solution 0.30 g
  • a coating solution was prepared in the same manner as in Example 1 except that. In the coating solution, when the mass of the silicon oxide component contained in the hydrolyzable silicon compound converted to SiO 2 is 100 parts by mass, 1 part by mass of the aluminum chelate complex is contained.
  • the silicon oxide component contained in the solid content of the coating solution is 99.41% by mass in terms of SiO 2
  • the aluminum compound in terms of Al 2 O 3 is 0.17% by mass
  • the organic component the distribution of the aluminum chelate complex.
  • the organic component derived from the ligand was 0.43% by mass.
  • Example 3 a coating film was formed by the same procedure as in Example 1 except that the coating liquid of Example 3 described above was used, and the above-described characteristics were evaluated. The results are shown in Table 1.
  • Example 4 Preparation of coating solution> Hydrolyzed liquid A, 1-methoxy-2-propanol (solvent), aluminum chelate complex solution, hydrolyzed liquid A 60.00 g, 1-methoxy-2-propanol (solvent) 38.68 g, aluminum chelate complex solution 1.32 g
  • a coating solution was prepared in the same manner as in Example 1 except that. In the coating solution, when the mass of the silicon oxide component contained in the hydrolyzable silicon compound converted to SiO 2 is 100 parts by mass, 4.4 parts by mass of the aluminum chelate complex is contained.
  • the silicon oxide component contained in the solid content of the coating solution is 97.44% by mass in terms of SiO 2
  • the aluminum compound in terms of Al 2 O 3 is 0.72% by mass
  • the organic component the distribution of the aluminum chelate complex.
  • the organic component derived from the ligand was 1.84% by mass.
  • Example 4 a coating film was formed in the same procedure as in Example 1 except that the coating liquid of Example 4 described above was used, and the above-described characteristics were evaluated. The results are shown in Table 1.
  • the silicon oxide component contained in the solid content of the coating solution is 91.93% by mass in terms of SiO 2
  • the aluminum compound in terms of Al 2 O 3 is 2.27% by mass
  • the organic component the distribution of the aluminum chelate complex.
  • the organic component derived from the ligand was 5.80% by mass.
  • Comparative Example 1 a coating film was formed in the same procedure as in Example 1 except that the coating solution of Comparative Example 1 was used, and the above-described characteristics were evaluated. The results are shown in Table 2.
  • the coating solution when the mass of the silicon oxide component contained in the hydrolyzable silicon compound converted to SiO 2 is 100 parts by mass, 13.1 parts by mass of aluminum chloride is contained.
  • Example 1 a coating film was formed in the same procedure as in Example 1 except that the coating liquid of Reference Example 1 was used, and the above-described characteristics were evaluated. The results are shown in Table 2.
  • the film was formed under the same heating conditions (heated cloth drying) as in Example 1, as shown in Table 2, the durability results evaluated by the pressure cooker test and the alkali resistance evaluation results were not good. Therefore, the heating for drying and curing the coating liquid applied to the glass plate is not performed using hot air, but the glass plate coated with the coating liquid is held in an electric furnace set at 400 ° C. for 4 minutes. Was done by. In the heating using this electric furnace, the maximum temperature reached on the glass surface on which the coating solution for the glass plate was applied was 300 ° C.
  • the glass plate after drying and curing was allowed to cool to room temperature, and a film was formed on the glass plate.
  • a glass plate provided with a coating formed by heating using this electric furnace was excellent in durability and alkali resistance evaluated by a pressure cooker test.
  • Table 2 the evaluation result of the glass plate provided with the film formed under the same heating conditions as in Example 1 is written together with “hot air drying”, and the film formed by heating using the above electric furnace The evaluation result of the provided glass plate is written together with “electric furnace drying”.
  • the coating solution when the mass of the silicon oxide component contained in the hydrolyzable silicon compound converted to SiO 2 is 100 parts by mass, 26.2 parts by mass of aluminum chloride is contained.
  • the silicon oxide component contained in the solid content of the coating solution was 83.33% by mass in terms of SiO 2
  • the aluminum compound in terms of Al 2 O 3 was 16.67% by mass
  • the organic component was 0% by mass. It was.
  • Example 2 a coating film was formed in the same procedure as in Example 1 except that the coating liquid of Reference Example 2 described above was used, and the above-described characteristics were evaluated. The results are shown in Table 2.
  • Table 2 the result of durability evaluated by the pressure cooker test and the result of alkali resistance evaluation were not good. Therefore, the heating for drying and curing the coating liquid applied to the glass plate is not performed using hot air, but the glass plate coated with the coating liquid is held in an electric furnace set at 400 ° C. for 4 minutes. Was done by. In the heating using this electric furnace, the maximum temperature reached on the glass surface on which the coating solution for the glass plate was applied was 300 ° C.
  • the glass plate after drying and curing was allowed to cool to room temperature, and a film was formed on the glass plate.
  • a glass plate provided with a coating formed by heating using this electric furnace was excellent in durability and alkali resistance evaluated by a pressure cooker test.
  • Table 2 the evaluation result of the glass plate provided with the film formed under the same heating conditions as in Example 1 is written together with “hot air drying”, and the film formed by heating using the above electric furnace The evaluation result of the provided glass plate is written together with “electric furnace drying”.
  • the transparent substrates with coatings of Examples 1 to 4 had a transmittance gain of 1.6% or more, and also had high durability and high alkali resistance.
  • the coated transparent substrates of Comparative Examples 1 to 3 have a high transmittance gain, but cannot satisfy both high durability and high alkali resistance, and are evaluated particularly in the pressure cooker test. It was inferior in durability.
  • a coated transparent substrate excellent in durability and alkali resistance can be provided.

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Abstract

La présente invention concerne un substrat transparent revêtu de film de revêtement qui comprend un substrat transparent et un film de revêtement qui est formé sur au moins une surface principale du substrat transparent. Le film de revêtement comprend : de la silice qui a une structure continue ; un composé d'aluminium ; et un composant organique. Le film de revêtement contient, en % en masse, plus de 93 % mais pas plus de 99,9 % de la silice qui a une structure continue, au moins 0,05 % mais moins de 2 % du composé d'aluminium en termes de Al2O3, et de 0,05 % à 5 % du composant organique. L'épaisseur de film du film de revêtement est de 20 à 500 nm. Le composant organique comprend un β-céto-ester.
PCT/JP2018/016162 2017-04-27 2018-04-19 Substrat transparent revêtu de film de revêtement, liquide de revêtement pour former un film de revêtement pour substrat transparent revêtu de film de revêtement, et procédé de production pour substrat transparent revêtu de film de revêtement Ceased WO2018198937A1 (fr)

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JP2019514445A JP7213177B2 (ja) 2017-04-27 2018-04-19 被膜付き透明基板、被膜付き透明基板の被膜を形成するための塗工液及び被膜付き透明基板の製造方法

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1152103A (ja) * 1997-07-30 1999-02-26 Fuji Photo Film Co Ltd 反射防止膜およびそれを配置した表示装置
JP2002022905A (ja) * 2000-07-04 2002-01-23 Jsr Corp 反射防止膜、反射防止膜を含む積層体、および反射防止膜の製造方法
JP2003327911A (ja) * 2002-05-15 2003-11-19 Dainippon Ink & Chem Inc 被膜の形成方法、該方法によって得られる被膜、反射防止膜及び光触媒膜
JP2009527786A (ja) * 2006-11-23 2009-07-30 エシロール アテルナジオナール カンパニー ジェネラーレ デ オプティック 二層構造の耐スクラッチおよび耐摩耗被膜を含む光学物品、およびこれを生産する方法
JP2015110313A (ja) * 2013-10-31 2015-06-18 セントラル硝子株式会社 親水性被膜形成物品、親水性被膜形成用塗布液及び親水性被膜形成物品の製造方法
WO2016051750A1 (fr) * 2014-09-30 2016-04-07 日本板硝子株式会社 Revêtement à faible réflexion, plaque de verre, substrat de verre, et dispositif de conversion photoélectrique

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1152103A (ja) * 1997-07-30 1999-02-26 Fuji Photo Film Co Ltd 反射防止膜およびそれを配置した表示装置
JP2002022905A (ja) * 2000-07-04 2002-01-23 Jsr Corp 反射防止膜、反射防止膜を含む積層体、および反射防止膜の製造方法
JP2003327911A (ja) * 2002-05-15 2003-11-19 Dainippon Ink & Chem Inc 被膜の形成方法、該方法によって得られる被膜、反射防止膜及び光触媒膜
JP2009527786A (ja) * 2006-11-23 2009-07-30 エシロール アテルナジオナール カンパニー ジェネラーレ デ オプティック 二層構造の耐スクラッチおよび耐摩耗被膜を含む光学物品、およびこれを生産する方法
JP2015110313A (ja) * 2013-10-31 2015-06-18 セントラル硝子株式会社 親水性被膜形成物品、親水性被膜形成用塗布液及び親水性被膜形成物品の製造方法
WO2016051750A1 (fr) * 2014-09-30 2016-04-07 日本板硝子株式会社 Revêtement à faible réflexion, plaque de verre, substrat de verre, et dispositif de conversion photoélectrique

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